EP0292120B1 - Procédé de fabrication de composition de résine polyester - Google Patents

Procédé de fabrication de composition de résine polyester Download PDF

Info

Publication number
EP0292120B1
EP0292120B1 EP88303697A EP88303697A EP0292120B1 EP 0292120 B1 EP0292120 B1 EP 0292120B1 EP 88303697 A EP88303697 A EP 88303697A EP 88303697 A EP88303697 A EP 88303697A EP 0292120 B1 EP0292120 B1 EP 0292120B1
Authority
EP
European Patent Office
Prior art keywords
polyester resin
titanium dioxide
process according
resin composition
kneading
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP88303697A
Other languages
German (de)
English (en)
Other versions
EP0292120A3 (en
EP0292120A2 (fr
Inventor
Kazuto Kiyohara
Toshiyuki Hagiwara
Takanori Nakadate
Ichiya Harada
Kentaro C/O Kanebo Ltd. Noguchi
Shigeru C/O Kanebo Ltd. Sakae
Kazuhiro C/O Kanebo Ltd. Okuma
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kanebo Ltd
Konica Minolta Inc
Original Assignee
Kanebo Ltd
Konica Minolta Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kanebo Ltd, Konica Minolta Inc filed Critical Kanebo Ltd
Publication of EP0292120A2 publication Critical patent/EP0292120A2/fr
Publication of EP0292120A3 publication Critical patent/EP0292120A3/en
Application granted granted Critical
Publication of EP0292120B1 publication Critical patent/EP0292120B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers

Definitions

  • the present invention relates to a process for producing a titanium dioxide containing polyester resin composition which may, for example, be used in the preparation of a reflective photographic support.
  • White inorganic pigments typified by titanium dioxide are conventionally dispersed in polyester resins typified by polyethylene terephthalate (PET) by either adding such pigments per se or by suspending them in an ester-forming polyhydric alcohol such as ethylene glycol to prepare a slurry and adding the slurry during esterification or polycondensation.
  • PET polyethylene terephthalate
  • the latter method is disclosed in many prior patents such as Japanese Patent Publication Nos. 945/1958 and 18135/1981.
  • this method has the problems that the particles of titanium dioxide added tend to agglomerate and precipitate in ethylene glycol or the resulting polymer, and that the amount of titanium dioxide that can be incorporated is no more than several percent.
  • 246236/1986 comprises dry blending a pigment with a polyester resin having a bulk density of no more than 0.6, blending them in molten state to prepare a master batch, and mixing the master batch with another feed of the polyester resin in molten state.
  • a polyester resin with a bulk density of no more than 0.6 and dry blending it with a pigment are quite cumbersome steps and the added pigment particles are frequently not uniformly dispersed in the resin.
  • the method disclosed in Japanese Patent Application (OPI) No. 250034/1986 comprises mixing a polyester resin with a pigment in molten state to prepare a master batch, subjecting the master batch to solid-phase polymerization, and mixing the resulting polymer with another feed of the polyester resin.
  • This method has the following disadvantages: the polymerization requires as long as 5 to 20 hours to complete; the method involves many steps; and, as in the first method, the added pigment particles are sometimes not uniformly dispersed in the polyester resins.
  • the two methods have a common problem in that the resin can pick up color as it is subjected to two cycles of blending in a molten state.
  • the present invention provides a process for producing a polyester resin composition by first supplying a polyester resin having an intrinsic viscosity of at least 0.40 and titanium dioxide having an average particle size of 0.1 to 0.5 ⁇ m and a water content of no more than 0.5%, the particles of which have been surface treated with an aluminum compound and/or a silicon compound, to a continuous kneading extruder, kneading them in the molten state such that the concentration of titanium dioxide is from 20 to 70 wt%, and then supplying an additional charge of the polyester resin to give a desired concentration of the titanium dioxide.
  • the process of the present invention provides a polyester resin composition having a high concentration of titanium dioxide dispersed uniformly, which composition can be produced in fewer steps and within a short period of time.
  • the continuous kneading extruder used in the process of the present invention may be of any type that permits continuous kneading and extrusion, such as an extruder equipped with a kneading rotor or blades, a corotating or counter-rotating twin-screw kneading extruder or a single-screw continuous kneader.
  • polyester resin used in the present invention may of course be a thermoplastic resin solely composed of a polyester. Included within the scope of the "polyester resin” are blends of a polyester and other polymers or additives that are incorporated in such amounts that the resin characteristics of the polyester as the chief component will not be affected for practical purposes.
  • Polyester resins that can be used in the present invention are polymers of the condensation products of aromatic dicarboxylic acids (e.g., terephthalic acid, isophthalic acid, phthalic acid and naphthalenedicarboxylic acid) and glycols (e.g., ethylene glycol, 1,3-propanediol and 1,4-butanediol); examples are polyethylene terephthalate, polyethylene 2,6-dinaphthalate, polypropylene terephthalate, polybutylene terephthalate, and copolymers thereof.
  • PET Polyethylene terephthalate
  • the polyester which is first supplied in the process of the present invention has an intrinsic viscosity of at least 0.40, preferably from 0.50 to 1.20, more preferably from 0.60 to 1.00.
  • intrinsic viscosity used herein means the value as measured at 20°C on a solution of the polyester resin in a mixed solvent of phenol and 1,1,2,2-tetrachloroethane in a 60:40 weight ratio, and is hereinafter abbreviated as IV.
  • the titanium dioxide used in the present invention is preferably of the rutile and/or anatase type.
  • the titanium dioxide has an average particle size of 0.1 to 0.5 ⁇ m. Particles whose size is outside this range will not provide a satisfactory degree of whiteness or hiding power.
  • the average particle size of the titanium dioxide can be measured by any known method such as electron microscopy or a precipitation technique.
  • the titanium dioxide particles used in the present invention have been surface treated with an aluminum compound and/or a silicon compound.
  • the surface treatment is performed in order to impart affinity for the polyester resin by treating the particles of titanium dioxide with an aluminum compound (e.g. alumina) and/or a silicon compound (e.g. silica) that has an oxygen or hydroxyl bond.
  • the titanium dioxide may be subjected to further surface treatments with metal soaps (e.g. zinc stearate, magnesium stearate and sodium palmitate), surfactants (e.g.
  • alkylene oxide derivatives aliphatic acid esters of polyhydric alcohols, quaternary ammonium salts, alkyl sulfate esters and amino acids), silane and titanium coupling agents, silicone oil, alcohols (e.g. methanol and ethanol) and polyhydric alcohols (e.g. ethylene glycol).
  • the titanium dioxide used in the present invention has a water content of no more than 0.5%.
  • the polyester resin when mixed with the titanium dioxide in the molten state, will undergo hydrolysis by the water in the latter. Another reason why titanium dioxide containing more than 0.5% water should not be used is that the particles with such a high water content will readily agglomerate to form coarse particles.
  • the titanium dioxide is surface-treated in order to provide it with affinity for the polyester resin.
  • the surface treatment is such that the water content of the titanium oxide is held at no more than 0.5%.
  • the concentration of the titanium dioxide lies is from 20 to 70 wt%.
  • Titanium dioxide may be used in combination with other pigments in the process of the present invention, such as barium sulfate, silica, alumina, talc and calcium carbonate, either on their own or as admixtures.
  • additives in common use such as brighteners, dyes, uv absorbers, antistats and antioxidants, may also be incorporated in amounts that will not be detrimental to the object of the present invention.
  • Polymeric materials other than polyesters can also be added; examples are polyolefins such as polyethylene and polypropylene.
  • the polyester resin and titanium dioxide supplied to the continuous kneading extruder are subjected to a kneading action in a zone equipped with kneading disks or rotor blades.
  • a kneading zone high temperatures occur because of the heat generated by the shearing action so the barrel is preferably cooled with water.
  • an additional feed of a polyester resin is supplied to the continuous kneading extruder.
  • the IV of the additionally supplied polyester resin is not limited to any particular value, but the IV of the initially supplied polyester resin and that of the additionally supplied polyester resin are preferably selected to produce maximum kneading effects while preventing the deterioration of the resins.
  • the IV of the initially supplied polyester resin may or may not be the same as that of the additionally supplied polyester resin.
  • the process of the present invention is especially useful in the production of polyester resin compositions having high concentrations of titanium dioxide, so the amount of the additional feed of the polyester resin is determined such that the finally obtained resin composition has a titanium dioxide concentration, for example, in the range of 10 to 50 wt%.
  • the polyester resin used in the present invention may be charged into the continuous kneading extruder either in a solid or molten state.
  • the additionally supplied polyester is preferably added in a state because this permits the temperature of the resin to drop when melted.
  • the continuous kneading extruder may be furnished with a kneading unit (e.g. a kneading disk) or an air vent that come into play in the period from the supply of the additional charge of polyester resin to the delivery of the resin composition.
  • a kneading unit e.g. a kneading disk
  • an air vent that come into play in the period from the supply of the additional charge of polyester resin to the delivery of the resin composition.
  • a polyester resin composition having a high concentration of titanium dioxide uniformly dispersed therein emerges from the continuous kneading extruder.
  • the composition, as it emerges from the extruder, may be fed into a film forming apparatus either directly or after having been shaped into chips.
  • the chips are preferably formed into a film after they are subjected to a heat treatment as described in Japanese Patent Application (OPI) Nos. 184538/1986 and 186957/1986.
  • Films can be produced by any known method such as the one described in Japanese Patent Application (OPI) No. 118746/1986.
  • the film thus produced is useful as a reflective photographic support.
  • Prior patents such as Japanese Patent Application No. 118746/1986.
  • the type of titanium dioxide used are defined in Table 1.
  • the kneading conditions are set forth in Table 2, in which Nos. 1 and 2 are samples used according to the present invention and Nos. 3 - 7 are comparative samples.
  • the TiO2 containing polyester compositions that had been passed through the kneading stage were discharged from the twin-screw kneading extruder, cooled with water and shaped into square pellets (3 mm x 3 mm x 3 mm).
  • a pellet was taken from each sample, melted on a glass plate, spread in a thin film and observed under a microscope (X100) to count the number of coarse ( ⁇ 20 ⁇ m) particles. Five measurements were made and their average was taken.
  • Pellets of sample Nos. 1 and 2 were heated at 220°C for 6 hours at 133 Pa (1 Torr) and fed to an extruder at 290°C, from which the extrudates were brought into contact with a rotating chill drum to form amorphous sheets 1.1 mm thick.
  • Each of the sheets was stretched first longitudinally at a draw ratio of 3.0 at 100°C, then transversely at a draw ratio of 3.0 at 110°C.
  • the drawn sheets were heat-set at 200°C, cooled and wound up.
  • the thus prepared films had a thickness of 125 ⁇ m and were white and opaque.
  • the drawing and shaping operations could be performed in a continuous stable manner.
  • the films had a sufficient degree of whiteness and opacity to be useful as reflective photographic supports.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Claims (8)

  1. Procédé de fabrication d'une composition de résine polyester dans lequel on fournit en premier une résine polyester ayant une viscosité intrinsèque d'au moins 0,40 et du dioxyde de titane ayant une taille particulaire moyenne de 0,1 à 0,5 µm et une teneur en eau ne dépassant pas 0,5%, dont les particules ont été traitées à leur surface avec un composé d'aluminium et/ou un composé de silicium, dans une extrudeuse à pétrissage continu, on les pétrit à l'état fondu de manière que la concentration de dioxyde de titane soit de 20 à 70% en poids, puis on fournit une charge additionnelle de la résine polyester pour donner la concentration désirée de dioxyde de titane.
  2. Procédé selon la revendication 1 dans lequel ladite résine polyester est le téréphtalate de polyéthylène, le 2,6-dinaphtalate de polyéthylène, le téréphtalate de polypropylène ou le téréphtalate de polybutylène.
  3. Procédé selon la revendication 2 dans lequel ladite résine polyester est le téréphtalate de polyéthylène.
  4. Procédé selon l'une quelconque des revendications 1 à 3 dans lequel la résine polyester fournie en premier a une viscosité intrinsèque de 0,50 à 1,20.
  5. Procédé selon la revendication 4 dans lequel la résine polyester fournie en premier a une viscosité intrinsèque de 0,6 à 1,00.
  6. Procédé selon l'une quelconque des revendications 1 à 5 dans lequel ledit composé d'aluminium est l'alumine.
  7. Procédé selon l'une quelconque des revendications 1 à 5 dans lequel ledit composé de silicium est la silice.
  8. Procédé selon l'une quelconque des revendications 1 à 7 dans lequel la concentration dudit dioxyde de titane dans la composition de résine polyester finale est de 10 à 50% en poids.
EP88303697A 1987-04-23 1988-04-25 Procédé de fabrication de composition de résine polyester Expired - Lifetime EP0292120B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP100917/87 1987-04-23
JP62100917A JPH083035B2 (ja) 1987-04-23 1987-04-23 ポリエステル樹脂組成物の製造方法

Publications (3)

Publication Number Publication Date
EP0292120A2 EP0292120A2 (fr) 1988-11-23
EP0292120A3 EP0292120A3 (en) 1989-02-22
EP0292120B1 true EP0292120B1 (fr) 1992-07-22

Family

ID=14286692

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88303697A Expired - Lifetime EP0292120B1 (fr) 1987-04-23 1988-04-25 Procédé de fabrication de composition de résine polyester

Country Status (4)

Country Link
US (1) US4877819A (fr)
EP (1) EP0292120B1 (fr)
JP (1) JPH083035B2 (fr)
DE (1) DE3872939T2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005035642A1 (fr) * 2003-10-10 2005-04-21 Commonwealth Scientific And Industrial Research Organisation Polymeres resistant a l'usure

Families Citing this family (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5252658A (en) * 1987-05-15 1993-10-12 Felix Schoeller Jr Gmbh & Co. Kg Pigment-containing premixture of titanium dioxide with olefin polymer
JPH02235045A (ja) * 1989-03-08 1990-09-18 Konica Corp 写真用反射支持体
US5180658A (en) * 1989-03-16 1993-01-19 Konica Corporation White polyester composition and support for photography
JPH02248456A (ja) * 1989-03-22 1990-10-04 Konica Corp 白色ポリエステル組成物および写真用支持体
US5281379A (en) * 1989-04-05 1994-01-25 Kanebo, Ltd. Processes for manufacturing thermoplastic resin compositions
JP2888656B2 (ja) * 1991-03-04 1999-05-10 ポリプラスチックス株式会社 着色熱可塑性樹脂組成物
MY109261A (en) * 1991-09-27 1996-12-31 Kerr Mc Gee Chem Corp Attenuation of polymer substrate degradation due to ultraviolet radiation.
US5352725A (en) * 1991-09-27 1994-10-04 Kerr-Mcgee Chemical Corporation Attenuation of polymer substrate degradation due to ultraviolet radiation
US5536793A (en) * 1993-01-29 1996-07-16 Amoco Corporation Concentrate for use in the melt fabrication of polyester
US5607994A (en) * 1994-02-28 1997-03-04 E. I. Du Pont De Nemours And Company Processibility and lacing resistance when silanized pigments are incorporated in polymers
JP3614941B2 (ja) * 1995-08-04 2005-01-26 富士写真フイルム株式会社 写真印画紙用支持体
US6126915A (en) * 1995-12-27 2000-10-03 Tohkem Products Corporation Titanium dioxide reduced in volatile water content, process for producing the same, and masterbatch containing the same
US5837757A (en) * 1996-06-18 1998-11-17 Idemitsu Petrochemical Co., Ltd. Flame-retardant polycarbonate compositions
TW462977B (en) * 1996-06-28 2001-11-11 Toray Industries Resin compositions, processes for producing thereby, and process for producing titanium oxide
JP3140373B2 (ja) 1996-07-05 2001-03-05 帝人株式会社 ポリエステル組成物およびその製造方法
DE69722531T3 (de) * 1996-08-30 2007-05-16 Mitsubishi Polyester Film Corp. Verfahren zur Herstellung einer Polyesterzusammensetzung
JPH11172082A (ja) * 1997-11-10 1999-06-29 Teijin Ltd 改質ポリエステルの連続製造方法
JP4010667B2 (ja) * 1998-10-08 2007-11-21 帝人ファイバー株式会社 ポリエステル樹脂組成物の製造方法
AU774558B2 (en) * 1999-09-14 2004-07-01 Ishihara Sangyo Kaisha Ltd. Titanium dioxide pigment, process for producing the same, and resin composition containing the same
DE10002164A1 (de) * 2000-01-20 2001-07-26 Mitsubishi Polyester Film Gmbh Weiße, UV-stabilisierte, thermoformbare Folie aus einem kristallisierbaren Thermoplast, Verfahren zu ihrer Herstellung und ihre Verwendung
CN100441408C (zh) * 2002-03-04 2008-12-10 威士伯来源有限公司 高反射率聚酯涂层
JP2005096384A (ja) * 2002-12-06 2005-04-14 Fuji Photo Film Co Ltd インクジェット記録用媒体及びインクジェット記録方法
US7265176B2 (en) * 2005-01-31 2007-09-04 E. I. Du Pont De Nemours And Company Composition comprising nanoparticle TiO2 and ethylene copolymer
JP4731245B2 (ja) * 2005-08-12 2011-07-20 倉敷紡績株式会社 軟質ポリウレタンフォームおよび化粧用部材
JP2007065065A (ja) * 2005-08-29 2007-03-15 Konica Minolta Opto Inc 光学フィルム、及びその製造方法
CN101378898A (zh) * 2006-02-02 2009-03-04 三菱树脂株式会社 隔热片
JP5217053B2 (ja) * 2007-04-06 2013-06-19 住化カラー株式会社 樹脂組成物の製造方法
US20100327728A1 (en) * 2009-06-30 2010-12-30 Sumitomo Chemical Company, Limited Method for producing resin composition, resin composition, reflection plate and light-emitting device
WO2012114895A1 (fr) * 2011-02-21 2012-08-30 積水化成品工業株式会社 Plaque de réflexion de lumière, composition de résine pour former la plaque de réflexion de lumière, et procédé de production de plaque de réflexion de lumière

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4309374A (en) * 1971-03-31 1982-01-05 Plastic Molders Supply Co., Inc. Method of coloring and molding a shaped thermoplastic resin article
US3770470A (en) * 1972-12-13 1973-11-06 Cabot Corp Pigmented resin compositions
EP0023387B1 (fr) * 1979-07-26 1984-02-22 Imperial Chemical Industries Plc Composition pigmentaire dispersable, sa préparation et son utilisation dans la coloration des matériaux thermoplastiques et peintures
JPS60245671A (ja) * 1984-05-21 1985-12-05 Ishihara Sangyo Kaisha Ltd 低次酸化チタン顔料
JPS61246236A (ja) * 1985-04-25 1986-11-01 Nippon Ester Co Ltd 原着ポリエステルペレットの製造法
JPS61250034A (ja) * 1985-04-27 1986-11-07 Nippon Ester Co Ltd 原着ポリエステルペレツトの製造法
FR2583424B1 (fr) * 1985-06-13 1987-07-31 Rhone Poulenc Fibres Melanges-maitres pour la matification de polyamides

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005035642A1 (fr) * 2003-10-10 2005-04-21 Commonwealth Scientific And Industrial Research Organisation Polymeres resistant a l'usure
US8093315B2 (en) 2003-10-10 2012-01-10 Commonwealth Scientific And Industrial Research Organisation Wear resistant polymers

Also Published As

Publication number Publication date
JPS63265948A (ja) 1988-11-02
EP0292120A3 (en) 1989-02-22
EP0292120A2 (fr) 1988-11-23
JPH083035B2 (ja) 1996-01-17
US4877819A (en) 1989-10-31
DE3872939T2 (de) 1993-02-04
DE3872939D1 (de) 1992-08-27

Similar Documents

Publication Publication Date Title
EP0292120B1 (fr) Procédé de fabrication de composition de résine polyester
US4898897A (en) Process for producing polyester resin composition
US3862084A (en) Preparation of polyethylene terephthalate containing inorganic fillers
JPH0768371B2 (ja) 二軸延伸ポリエステルフイルム
JPH0689160B2 (ja) 白色ポリエチレンテレフタレ−トフイルム
JPH0418525B2 (fr)
US3578730A (en) Thermoplastic polyester-poly-3-methyl butene-1 moulding compositions
JPH11505780A (ja) 結晶性熱可塑性樹脂の着色した非晶質シート
JPH11152324A (ja) 芳香族ポリエステルおよび二軸延伸ポリエステルフィルム
JP3593817B2 (ja) 白色ポリエステルフィルム
JP2582569B2 (ja) ポリエステル樹脂組成物の製造法
JP2519050B2 (ja) ポリエステル樹脂組成物の製造法
JPS61209260A (ja) 樹脂組成物の製造方法
KR101552429B1 (ko) 차광성 및 표면활성이 우수한 폴리에스테르 수지 및 그 제조방법
JPH09316386A (ja) 着色剤組成物およびその着色剤組成物を用いて成る成形物
JPH085978B2 (ja) 白色ポリエチレンテレフタレ−トフイルム
JPH09316387A (ja) 着色剤組成物およびその着色剤組成物を用いて成る成形物
JPH06271682A (ja) ポリエステル組成物の製造方法
JPH0665478A (ja) ポリエステルフイルム
JPH02248456A (ja) 白色ポリエステル組成物および写真用支持体
JP2003138112A (ja) ポリエステル組成物及びそれからなるフィルムまたはシート
JPH09227768A (ja) 着色剤組成物およびその着色剤組成物を用いて成る成形物
JPH1046096A (ja) 着色剤組成物およびその着色剤組成物を用いて成る成形物
KR19990055064A (ko) 2축배향 폴리에스테르 필름
JP2000017158A (ja) ポリエステル樹脂組成物およびそれを用いたフィルム

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): DE FR GB IT NL

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): DE FR GB IT NL

17P Request for examination filed

Effective date: 19890803

17Q First examination report despatched

Effective date: 19901207

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB IT NL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRE;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.SCRIBED TIME-LIMIT

Effective date: 19920722

Ref country code: NL

Effective date: 19920722

Ref country code: FR

Effective date: 19920722

REF Corresponds to:

Ref document number: 3872939

Country of ref document: DE

Date of ref document: 19920827

EN Fr: translation not filed
NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19930419

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19930506

Year of fee payment: 6

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19940425

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19940425

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19950103